Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
  • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
  • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups

Definitions

• the present invention is directed to an improved method of carrying out cationic polymerization of cyclic ethers to produce tetrafunctional polymers, particularly cationic polymerization of oxetanes and substituted and unsubstituted tetrahydrofuran.
• the invention is further directed to cured elastomers formed from such tetrafunctional polymers and to high-energy compositions utilizing such cured elastomers in binder systems.
• U.S. Patents No. 4,393,199 and 4,483,978 are directed to a method of cationic polymerization of cyclic ethers in which a polyhydric alcohol, e.g., a diol, is mixed with a cyclic ether monomer(s) and an acid catalyst.
• a polyhydric alcohol e.g., a diol
• Polyethers formed from oxetane and tetrahydrofuran (THF) monomers are also described, for example, in U.S. Patents No. 4,405,762 and 4,707,540, the teachings of which are incorporated herein by reference.
• Cross-linked elastomers are useful, for example, as elastomeric binders for high-energy compositions, such as propellants, gasifiers, explosives, or the like.
• high-energy compositions contain a cross-linked elastomer, solid particulates, such as fuel particulates and oxidizer particulates, and may also contain a plasticizer for the elastomer.
• U.S. Patent No. 4,393,199 describes a synthesis of polyoxetane or polyoxetane/tetrahydrofuran polymers by a cationic, living polymer process.
• a polyfunctional alcohol is reacted with an acid, e.g., a Lewis acid, such as boron trifluoride, to form an adduct.
• This adduct reacts with a cyclic ether, such as an oxetane or tetrahydrofuran (THF), activating the cyclic ether towards attack by an initiator alcohol or polymer terminal alcohol.
• THF oxetane or tetrahydrofuran
• the terminal end of the cyclic ether residue is an alcohol and, in a similar manner, attaches to a further activated cyclic ether molecule, opening the ring in the process.
• the functionality, particularly hydroxyl functionality, of the polymer which is produced corresponds to the hydroxyl functionality of the alcohol.
• the polyether which is produced has an hydroxyl functionality of about 2.
• the polymer has a hydroxyl functionality of about 3. Side reactions or incomplete initiation from all hydroxyl groups may result in a polymer which varies slightly from the functionality of the alcohol precursor.
• Cyclic ethers formed from oxetanes or oxetanes plus THF have important potential as binders for high-energy compositions, such as propellants, explosives, gasifiers, or the like.
• Cured polymers formed from oxetanes and/or THF are elastomeric material and are capable of carrying high levels of particulate materials, such as fuel particulates and/or oxidizer particulates.
• the high-energy plasticizers may be compatible with high levels of energetic plasticisers, e.g. nitrate ester plasticizers.
• oxetane and oxetane/THF polymers which have been used to form elastomeric binders are difunctional, e.g., having a pair of terminal hydroxyl groups.
• difunctional polymers must be cured with a curing agent, e.g., an isocyanate of functionality substantially higher than two.
• a mixed isocyanate curative sold under the tradename Desmodur N-100® having a functionality of about 3.6, is often used to cure difunctional oxetane and difunctional oxetane/THF polymers.
• a problem with elastomeric binders formed from oxetane and oxetane/THF polymers is their tendency to have mechanical characteristics less than that which would be desired for a high-energy composition, particularly for a rocket motor propellant. It is especially difficult to provide binders formed from oxetane and oxetane/THF polymers having adequate stress capabilities. Recently, it has been found that better stress capabilities are achieved using trifunctional polymers formed from oxetanes and oxetanes plus THF.
• U.S. Patent No. 4,393,199 suggests polymerization using tetrafunctional alcohol molecules, particularly pentaerythritol. Presumably, a living polymer grown from each hydroxyl group of the pentaerythritol molecule would produce a tetrafunctional polymer. However, it is believed that successful cationic polymerization from pentaerythritol has not been achieved. This is not to say that no molecules of tetrafunctional polymer have been produced by cationic polymerisation from pentaerythritol, but that a very substantial proportion of the polymer molecules produced have functionalities less than four. A major problem with using pentaerythritol is its relatively polar nature.
• oxygen-containing solvents are generally excluded, requiring the use of substantially non-polar solvents in which pentaerythritol is substantially immiscible. It is further believed that the close proximity of the four hydroxyl groups of pentaerythritol molecule often results in polymer chain initiation from less than all of the four hydroxyl groups.
• polymers having four terminal hydroxyl functions are produced from cyclic ethers, particularly oxetane, substituted oxetanes, tetrahydrofuran and substituted tetrahydrofurans.
• the tetrafunctional alcohol from which the polymer is grown is relatively non-polar (relative to pentaerythritol) and is, therefore, miscible in organic solvents in which cationic polymerization may be carried out.
• One suitable preinitiator is the tetraol 2,2'(oxydimethylene)bis(2-ethyl-1,3-propanediol).
• Synthesis of a tetrafunctional polymer is promoted by a low ratio of acid catalyst to tetraol; acid catalyst being used at a level of between about 0.05 and about 0.5 equivalents relative to the hydroxyl functional groups of the tetraol, i.e., between about 0.20 and about 2 equivalents per mole of tetraol.
• the tetrafunctional polymers may be cured, e.g., with polyfunctional isocyanates, to form elastomers.
• Such elastomers are useful for binder systems for high-energy compositions, such as propellants, explosives, gasifiers, or the like.
• the invention is directed to cationic polymerization of oxetane, substituted oxetanes, tetrahydrofuran, and substituted tetrahydrofurans, i.e., cyclic ethers having 4 and 5 member rings.
• Suitable substituted oxetanes and tetrahydrofurans are described, for example, in U.S. Patents No. 4,483,978 and 4,707,540, the teachings of which are incorporated herein by reference.
• Polymerizations in accordance with the invention may be conducted with a single monomer species or a mixture of monomer species. It is common, for example, to copolymerize THF and a substituted oxetane monomer.
• the R groups are the same or different and are selected from moieties having the general formulae: -(CH2) n X, where
• oxetanes used in forming block polymers in accordance with the invention include but are not limited to:
• the tetrafunctional polymers are grown from a tetrafunctional alcohol which is substantially less polar than pentaerythritol and, therefore, soluble in organic solvents in which polymerization may be carried out.
• Suitable solvents are non-protic, non-ether, inert solvents. Such solvents include, but are not limited to methylene chloride and chloroform.
• Tetraols useful in forming tetrafunctional polymers have the general formulae:
• R1 is a non-polar extender, e.g., an alkyl or ether moiety.
• R1 is saturated.
• R1 is a straight chain of from 1 to 3 carbon or oxygen atoms.
• the R2's are the same or different and each R2 is either nothing or a non-polar extender, e.g., an alkyl or ether moiety.
• R2 is -CH2- or -CH2-CH2-.
• the R3's are the same or different and each R3 is either nothing or a hydrocarbon chain, preferably saturated. Most preferably R3 is nothing, -CH2- or -CH2-CH2-.
• An advantage of having a relatively low molecular weight tetraol is that it does not substract significantly from the total energy of the polymer, whereas a larger molecular weight initiator, which is similarly non-energetic, would lower the total energy content of the polymer markedly.
• a particular suitable tetraol for use as a preinitiator species is 2,2'(oxydimethylene)bis(2-ethyl-1,3-propanediol) having the chemical formula: (V.W. Gash, Journal of Organic Chemistry , Vol. 37, p. 2197, (1972)).
• This tetraol is substantially less polar than pentaerythritol and largely dissolves, for example, in methylene chloride and chloroform.
• the hydroxyl moieties of the tetraol are less bunched together, better enabling cationic polymerization to proceed from each of the hydroxyl moieties.
• the molecular weight of the tetraol be relatively low, preferably under about 500, and more preferably, under about 300. It is desirable that the tetraol be as small a part of the polymer as possible so that its residue has only a minor effect on the characteristics of the polymer relative to the effects of the cyclic ether residues.
• oxetanes may be used having energetic pendant groups in order to contribute to the energy of a high-energy composition; tetraol molecules are substantially less energetic than many energetic oxetanes and therefore detract from the energy of the polymer as a whole.
• the acid catalysts may be chosen from among those known in the art, including Lewis acids, such as AlCl3, BF3, TiCl4, ZnI2, SiF4, SbF5, PF5, AsF5, and SbCl5, and strong proton acids, such as FSO3H, ClSO3H, HClO4, HIO4, and CF3SO3H.
• Lewis acids such as AlCl3, BF3, TiCl4, ZnI2, SiF4, SbF5, PF5, AsF5, and SbCl5, and strong proton acids, such as FSO3H, ClSO3H, HClO4, HIO4, and CF3SO3H.
• the acid catalyst is used at a much lower level relative to hydroxyl groups of the tetraol than is taught in the prior art.
• a ratio of diol to a Lewis Acid, i.e., butanediol to BF3-etherate to form a butanediol/BF3 initiator species should be about 1:2, which is about 1 mole of BF3 for each mole of hydroxyl groups.
• U.S. Patent No. 4,393,199 teaches that no polymerization occurs if the ratio of butanediol to BF3 is 1:1.
• a Lewis acid is used at a ratio relative to hydroxyl groups of the polyhydric alcohol of 0.5:1 or less, i.e., from about 0.05:1 to about 0.5:1.
• the acid catalyst is used at between about out 0.20 to 2 equivalents per mole of tetraol. If a proton acid is used as the initiator, the ratio of hydrogen ions released by the acid catalyst to the hydroxyl groups of the alcohol is from about 0.05:1 to about 0.5:1.
• a general procedure for polymer synthesis is as follows: The general amount of tetraol is slurried in dry CH2Cl2. To this is added 0.25 molar equivalents of BF3OEt2 (borontrifluoride-etherate). After about 30 minutes, the desired amount of oxetane monomer(s) and/or THF monomers are added dropwise. After the polymerization is judged to be complete the reaction is diluted with CH2Cl2 and saturated aqueous NaHCO3. The layers are separated and the aqueous layer washed with CH2Cl2. The combined organics are dried, and the solvent removed to afford the desired polymer.
• BF3OEt2 borontrifluoride-etherate
• Elastomers are formed from the tetrafunctional polyethers by curing with isocyanates having a functionality of at least two, e.g., toluene diisocyanate.
• a cross-linked density of at least about 10% is generally preferred in an elastomer to be used in a binder.
• One advantage of using tetrafunctional polymers to form elastomers is that it is frequently possible to use an isocyanate curing agent of low functionality to achieve the desired degree of cross-linking.
• an isocyanate curing agent of low functionality for example, it is common to use a mixed isocyanate curative having a functionality of about 3.5.
• a difunctional isocyanate such as toluene diisocyanate (TDI) or hexamethylenediisocyanate (HDI).
• TDI toluene diisocyanate
• HDI hexamethylenediisocyanate
• Propellant compositions comprise between about 50 and about 90 weight percent particulate solids, including fuel material particulates and oxidizer particulates. The balance is substantially all a binder system which comprises the cured elastomeric binder and which may include a plasticizer.
• a typical particulate fuel material is aluminum.
• Particulate oxidizer materials include but are not limited to ammonium perchlorate (AP), cyclotetrdmethylene tetranitramine (HMX), cyclotrimethylene trinitramine (RDX), and mixtures thereof.
• AP ammonium perchlorate
• HMX cyclotetrdmethylene tetranitramine
• RDX cyclotrimethylene trinitramine
• the invention herein is further intended to encompass high-energy compositions, such as propellant compositions formed from the tetrafunctional polymers.
• the binder system of the high-energy composition may include an energetic plasticizer, particularly a nitrate-ester plasticizer.
• Nitrate ester plasticizers include, but are not limited to nitroglycerin (NG); mono-, di-, and triethyleneglycol dinitrate, butanetriol trinitrate (BTTN); and trimethylolethane trinitrate (TMETN). If the polymer is compatible with a nitrate ester plasticizer, amounts of the plasticizer approaching the limits of retention in the binder system may be used. Typically the weight ratio of plasticizer to polymer is up to about 2.5:1.
• the desired overall amorphous character in this tetrafunctional poly-BAMO/NMMO was achieved by the timed addition of NMMO (the more reactive monomer) to the reaction solution containing BAMO (the less reactive monomer) and a portion of the NMMO.
• the observed relative percentages of BAMO and NMMO incorporated were determined by the feed ratio. Either a methanol or an acetonitrile liquid/liquid extraction is used to purify the polymer, thereby helping to ensure a low extractables content.
• R. Wardle and R. Biddle A Report on the Synthesis and Scale-Up Chemistry of Polyoxetane Thermoplastic Elastomers , BRL Contract DAAA15-85-C-0037, 16 Dec 1987 and J.
• the target molecular weight (MW) was determined by dividing the grams of monomer by moles of initiator.
• the vapor phase osmometry (VPO) molecular weight was measured in chloroform on a Knauer VPO calibrated with benzil using three concentrations of polymer ranging from 10 to 50 g per liter and is corrected for small amounts of oligomer and monomer.
• the equivalent weight (eq wt) was determined using an isocyanate titration method and by NMR endgroup analysis.
• the percentage of initiator incorporated (init. inc.) was determined by NMR comparison of the polymer backbone and initiator resonances in the polymer.
• the percentage of chains with an initiator was determined by NMR comparison of end-group-to-initiator absorbencies.
• Mw, Mn and polydispersity were determined by GPC using poly(glycol-adipate) as calibration standard with a series of four columns from 100 to 100,000 angstroms employed for separation. Two measures of functionality are given, one based on osmometry and titration equivalent data and the other on NMR data. Taken in sum, the data in this table constitute irrefutable proof that the materials possess a functionality of four and were synthesized in a controllable manner.
• the initiator system results in molecular weight control being influenced strongly by the monomer/initiator ratio and has been shown experimentally to exhibit the characteristics of a "pseudo-living polymerization" mechanism.
• small aliquots were removed and quenched at several stages of the polymerization.
• the polymers were analyzed, and analysis gave a profile of the progression of the reaction.
• the molecular weight was shown to increase linearly with conversion and a high percentage of the initiator was incorporated into the polymer early in the polymerization with exactly one initiator incorporated per polymer chain.
• Knowing the critical parameters defining the mechanism of the polymerization has enabled both polymer functionality and molecular weight to be controlled, as well as other important polymer parameters (e.g., polydispersity, relative monomer incorporation, and amorphous character). This control has been verified by producing a number of energetic oxetane polymers of varying molecular weight and functionality.

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• Polymers & Plastics (AREA)
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• 1989
  • 1989-03-14 US US07/323,587 patent/US5099042A/en not_active Expired - Fee Related
• 1991
  • 1991-09-12 CA CA002051267A patent/CA2051267A1/en not_active Abandoned
  • 1991-09-12 EP EP91308336A patent/EP0531591A1/de not_active Withdrawn
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  • 1991-10-01 JP JP3253688A patent/JPH05117384A/ja active Pending

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